Electric accumulator.



M. G. THIELLET & M. J. DENARD.

ELECTRIC AGQUMULATOR. APPLICATION FILED APR. 3, 1907.

,FIGZ) l/v \IE/V TOPS Patented Oct. 13,1908.

' ,the following is a specification.

UNITED. STATES PATENT OFFICE.

MOLIERE CHARLES THIELLET AND MARlUS JOSEPH DENARD, 0F LYON, FRANCE.

ELECTRIC ACOU'MULATOB.

' Specification of Letters Patent.-

Patented Oct. 1a, 1908.

Application filed April 8, 1907. Serial No. 866,240.

To all whom it may concermj' Be it known that we, MoLnJRE CHARLEs THIELLET and MARIUS Josnrn DENARD, citizens of the French Republic, residing at Lyon, in-France, have invented a certain new and useful Electric Accumulator, of which This invention relates to improvements in electric accumulators and .its purpose is to increase the life and efliciency of such accumulators. This ob'ect is attained by securing more perfect a herence and conductive connection between the active mass and the carriers thereof by rendering the said mass harder and less liable to disinte ration, by securing more complete and un' orm chemical action in order to revent distortion of the plates, and by fac' ltating the circulation of the electrolyte andthe escape of the gases evolved.

The active mass used at the negative electrodes of the improved accumulator-is a mixture of lead OXld, minium, sulfate of magnesium and gelatinous bichromated silicate, good results being obtained by using 80 arts lead oxid, 10 parts minium, 10 arts su ate of magnesium, with gelatinous ichromated silicate added to form a paste.

The active .mass used at the ositive electrodes is a mixture of lead oxi chemically produced peroxid of lead, sulfate of magnesium, granular umice stone; and elatinous bichromated s lcate, good results eing obtained by using 80 parts peroxid'of lead, 10 parts lead oxid, 5 parts pumice stone, 5 parts sulfate of magnesium, with elatinous bichromated silicate added to orm a paste. The proportions here indicated for the constituents of the negative and ositive masses may, however, be varied wit in certain limits not exceeding, in general, an increase or decrease of ten per cent.

The cementitious substance referred to as gelatinous bichromated silicate, which is insoluble in dilute and concentrated sulfuric acid, is used to render the active mass hard and adhesive and is prepared in the following manner.

Asbestos board or cord is boiled for approximately twohours in dilute sulfuric acid of density 1.10, and is by this means disintegrated and converted into a aste or emulsion of asbestos fiber, which'is filtered and washed to remove all traces of acid. 250

grams of this fibrous asbestos are then mixed with 9 liters of sulfuric acid of density 1.22, the mixture being stirred to render it homogeneous, w1th,the addition of 2 liters of silicate of soda of density 1.20. Before the silicate of soda is added it is freed from chlorin by the following dprocess. Eglual quantities o silicate of so a and dist' ed water are mixed'in an iron vessel 'and a porous pot containing equal uantities of silicate of soda and caustic potas (of density 1.22 to 1.25) is placed therein, the li uids in the outer and inner vessel being at t e same level and an iron plate being placed in the porous pot to act as an anode, with the outer vesselactin as a cathode. Electric current is then caused to flow through this cell, and the action thereof causes the chlorin to pass into the anodechamber, in which it is absorbed by the caustic soda.

The mixture of 2 50 ams asbestos fiber, 9 liters sulfuric acid, 2 filers silicate of soda, is agitated until it becomes as fluid as possible and acquires an oily appearance. To thismixture are added 60 or 70 per cent. of bichromated gelatin prepared by mixing 120 ams gelatin, 1440 grams water, 24 grams ichromate of otash, 10'cubic centimeters of ammonia. e gelatin is caused to absorb water at a'temperature of 60 degrees centigrade, and this water is then pressed out and replaced b fresh water at the same temperature, whic is then also pressed out, and the same operations are repeated a third time, the purpose being to remove from the gelatin impurlties, for example fatt admixtures. The quantity of water whic may be used for, this purpose is, of course, not restricted to any definite prolportlon. The

water to be mixed with the e atin is cured over the latter while the ge atin is sti wet, and the water and gelatin are then placed over a Bunsen burner and raised to a temperature of 80 centigrade, at which the gelatin is dissolved. When the solution is clear, without solid nuclei therein, the bichromate of potash is added thereto ina finely pulverized state, Thereupon the mixture is filtered and the ammoniaiis added.

The paste must be pre ared immediately after the preparation of the gelatinous mixture, since the latter rapidly becomes hard. A mixture of elatinous mass and active mass, dried ,an exposed to the sun for an cold water and in dilute and concentrated sulfuric acid. This paste is powerfully pressed in molds of s ecial construction which will be describe hereinafter. The cementation obtained by means of the gelatinous mixture roduces perfect cohesion of the particles. The plates are dried in a dark place at a constant temperature of 18 degrees centigrade, and are then exposed to the sun-1i ht for a period depending on the deee of durability which it is desired to secure. t has been found that ex osure for 80 minutes produces a sufficient egree of durability without deteriorating the capacity in am pere-hours. By increasing the proportion of potassium bichromate the hardness of the mixture is increased, but the ca acity is at the same time reduced. For t e positive electrodes pure peroxid of lead is more suitable than any other oxid of lead.

In order that the formation may take lace under favorable conditions it is essentia that the paste has sufficient conductivity, and this is nearly always the case. If, however, a too large proportion of dioxid of lead is used, for example more than 90 per cent. the conductivity may be too low, and the formation only takes place rogressively from the conductor towards t e center of the mass, more articularly if the pockets in the plates are arge. The rate of formation is in that case low, the greater part of the current being.

used to electrolyze the sulfuric acid, and the adhesion of the peroxid is not very perfect. To obviate this disadvantage a aste containing eroxid of lead is used. he formation in t at case goes to a greater depth, and the len th of time required therefor is considerabfy reduced.

The active mass is compressed in a mold which imparts to it the sha e of an embossed late, one side of which is s iown in Figure 1. he two sides of the plate are identical, but the arrangement of the circular bosses a and b is such that the bosses at on either side are coaxial with the bosses b of smaller diameter on the other side. The plate is provided with small holes 0 made at the bases of rectangular recesses d. The longer sides of the recesses d on one side of the plate are perendicular to the longer sides of the recesses s on the other side of the plate.

The metallic support or carrier of the active mass is cast on the plate, so that molten metal flows through the holesc and forms as it were tenons which connect the two parts of the carrier. Fig. 2 shows the carrier, with the active mass removed.

For casting the carrier the plate of active mass is placed in a mold consisting of two symmetrical parts. The casting is erformed at a high temperature so that su semoses quently the metal contracts considerably and is thus pressed tightly against the active mass. Homogeneousness is secured by introducin compressed air, by which the metal is orced into the small cavities and re cesses.

An indefinite number of electrodes thus produced may be joined up together, accordmg to the ca acity of the battery to be roduced. For farge batteries or portable atteries the electrodes may be soldered or sealed into frames of the same metal or metallic composition as the carrier. Fi 3 represents a frame for three electrode ates.

The carrier consists of an alloy tfie ingredients of which are as follows ead 83 per cent. antimony 7 per cent., zinc 10 per cent. subject, however, to variations in the proportions of the constituents. The percentage of lead may vary between 80 and 90, that of antimony between 5 and 10, and that of zinc between 8 and 15. The hardness, lightness and porosity of the carrier depend on the choice of these proportions. The specific proportions indicated give good results for avera e requirements.

From t e positive plates the zinc must be eliminated. This is effected in the following manner. The plates are placed in a receptacle containing sulfuric acid 12 grams, water 88 grams. Into this receptacle is placed a porous pot containing a carbon plate and nitric acid at 30 or 40 degrees Baum, the purpose of the latter being to act as a depolarizer. The composite plates are then connected to the carbon plate, whereupon the zinc is dissolved in the sulfuric acid; the hydrogen evolved by the decomposition of the water reduces the nitric acid, water and nitric peroxid being formed. By the elimination of the zinc the carrier is rendered porous, which is an advantage, the weight being reduced and the surface for contact with the electrolyte being increased. At the same time the sulfate of magnesium in the active mass is disintegrated and removed, so that theactive mass becomes porous.

In the case of the negative electrodes the presence of the zinc is an advantage and has been found to increase the electromotive force 0.5 volt.

At the beginning of the discharge curve there is a sharp drop from 2.8 volts to 2.5 volts; thereupon the e. m. f. becomes constant and remains during normal discharge at between 2.4 and 2.3 volts. From this value the e. m. f. does not drop suddenly to zero, but remains for a very considerable time between 0.6 and 0.4 volts. The drop from 0.6 volt to zero occupies a longer period than the drop fom the normal e. m. f. (2.4 or 2.3 volts) to 0.6 volt, and the slope of the curve is steep at the end. The malntenance of the electromotive force at a value varying from 0. 6 to 0.4 volt is explained by the f 1 lowing reactions At the end of this discharge the normal ac- .tion of the positive electrode ceases, but if there is still an excess of zinc present a new couple comes into action, the lead sulfate becoming the positive electrode and producing with the zinc an electromotive force of approximately 0.5 volt, the reaction being as fol ows: Y

1 5 Zn H2804 PbSO znso H2804 Pb,

the specific capacity is increased, the electrochemical equivalent of zinc being smaller than that of lead. Moreover, the resence of zinc renders the sulfating of the p ates impossible.

What we claim as our invention and desire to secure by Letters Patent of the United States is:-

In an electric accumulator an electrode comprising in combination with theoxid of lead, gelatin gelatinized in'a ueous bichromate of potash, and asbestos ber emulsified.

in sulfuric acid and silicate of soda.

In witness whereof we have signed this specification in the presence of two Witnesses.

mourns CHARLES THIELLET. MARIUS JOSEPH DENARD. Witnesses:

Gns'roN ZEAUNIAUX, Tnos. N. BROWNE. 

